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64.
Beck R Deek J Choi MC Ikawa T Watanabe O Frey E Pincus P Safinya CR 《Langmuir : the ACS journal of surfaces and colloids》2010,26(24):18595-18599
We present persistence length measurements on neurofilaments (NFs), an intermediate filament with protruding side arms, of the neuronal cytoskeleton. Tapping mode atomic force microscopy enabled us to visualize and trace at subpixel resolution photoimmobilized NFs, assembled at various subunit protein ratios, thereby modifying the side-arm length and chain density charge distribution. We show that specific polyampholyte sequences of the side arms can form salt-switchable intrafilament attractions that compete with the net electrostatic and steric repulsion and can reduce the total persistence length by half. The results are in agreement with present X-ray and microscopy data yet present a theoretical challenge for polyampholyte interchain interactions. 相似文献
65.
An experimental and theoretical study was conducted of the column characterization technique in which plate heights determined using the conventional pulse-response method are compared with those determined using a bi-directional method where an eluite sample is introduced into one end of a chromatographic column and elution occurs at the same end after the flow direction is reversed inside the column. Experiments are presented for a micropellicular HPLC column before and after its performance has been degraded by repeated sample injections, for a low-pressure column containing nonporous glass particles, and for an HPLC column containing particles with 300 Å pores. The results obtained are interpreted in terms of several different theories which apply in various Fourier number ranges. It was shown that the transcolumn contribution to convective dispersion in a chromatographic column is largely responsible for the difference observed between conventional and bi-directional plate-height measurements and that a collocation method can be employed to develop a useful analytical expression for this contribution. 相似文献
66.
In this paper, we propose a nonlinear PDE model for reconstructing a regular surface from sampled data. At first, we show the existence and the uniqueness of a viscosity solution to this problem. Then we propose a numerical scheme for solving the nonlinear level set equation on unstructured triangulations adapted to the data sample. We show the consistency of this scheme. In addition, we show how to compute nodewise first and second order derivatives. Some application examples of curve or surface construction are provided to illustrate the potential and to demonstrate the accuracy of this method. 相似文献
67.
Ethylene diamine (EDA)/salt solvent systems can dissolve cellulose without any pretreatment. A comparison of the electrical
conductivity of different salts in EDA was made at 25 °C, and conductivity decreased in the order of KSCN>KI>NaSCN at the
same molar concentration. Among the salts tested, potassium thiocyanate (KSCN) was capable of dissolving both high molecular
weight (DP>1000) and low molecular weight (DP = 210) cellulose, and this was confirmed by polarized light microscopy. 39K and 14N NMR experiments were conducted at 70 °C as a function of cellobiose concentration with EDA/KSCN as the solvent. The results
showed that the K+ ion interacts with cellobiose more than the SCN− ion does. Recovered cellulose was studied by infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). Changes
in the FTIR absorption bands at 1,430 and 1,317 cm−1 were associated with a change in the conformation of the C-6CH2OH group. The changes in positions and/or intensities of absorption bands at 2,900, 1,163, and 8,97cm−1 were related to the breaking of hydrogen bonds in cellulose. X-ray diffraction studies revealed that cellulose, recovered
by precipitating cellulose solutions with water, underwent a polymorphic transformation from cellulose I to cellulose II. 相似文献
68.
Pfaffen C Infanger D Ottiger P Frey HM Leutwyler S 《Physical chemistry chemical physics : PCCP》2011,13(31):14110-14118
The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ~6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations. 相似文献
69.
Taking the regio‐ and chemoselectivities of our iron complex precursors with pyridine core in aerobic oxidations into account, we envisioned a more effective influence on catalytic properties by the introduction of different substituents in 4‐position of the pyridine moiety. The synthesis of these novel 4‐substituted (pyridine‐2,6‐diyl)dipropanoic acids 4 is described. Analogously to the unsubstituted derivative, ligands 4 reacted with Fe(ClO4)3 to form trinuclear Fe3(μ3‐O) complexes 3 , which were tested in the aerobic Gif‐type oxidation of α‐pinene to myrtenol, verbenone, myrtenal, and pinene oxide. The electronic nature of the substituents was found to slightly effect the ratio of allylic oxidation/epoxidation, whereas its influence on the oxidation preference of secondary to primary C? H bonds is negligible as compared to the unsubstituted complex. 相似文献
70.
W.P. RDZANEK JR 《Journal of sound and vibration》2002,249(2):307-323
The standardized mutual active and reactive sound power of a clamped plate, representing the energy aspect of the reciprocal interactions of two different in vacuo modes, has been computed. It was assumed that the vibrations are axisymmetric, elastic and time harmonic, the plate's transverse deflection is small as compared with the plate's size, and that the vibration velocity is small as compared with the acoustic wavenumber generated. The Kirchhoff-Love theory of a perfectly elastic plate was used. The integral formulae for the mutual sound power were transformed into their Hankel representations which made possible their subsequent computation. A closed path integral was used to express the integral in its Hankel representation to compute the mutual active sound power. The asymptotic stationary phase method was used to compute the two magnitudes, i.e., the mutual active and reactive sound power. The results obtained are the asymptotic formulae valid for the acoustically fast waves. The oscillating as well as the non-oscillating terms have been identified in the formulae to make possible their further separate analysis. The availability of the asymptotic formulae makes possible some fast numerical computations of the mutual sound power. Moreover, the formulae presented herein, together with those for the individual modes known from the literature, make a complete basis for further computations of the total sound power of the plate's damped and forced vibrations in fluid. 相似文献